CLASS - XII
SUBJECT – CHEMISTRY
GIST OF CHAPTER –THE d
AND f BLOCK ELEMENTS
(v) Trends in the M2+/ M standard electrode potentials: EoM2+/M is governed by three
factors. Enthalpy of sublimation, enthalpy of ionisation and enthalpy of hydration. The
irregular trend in 3d series is due to irregular variation in ionisation enthalpy and heat of
sublimation.
(vi) Density d-block elements have high density because of their small atomic size and strong
metallic bonding. Osmium has slightly lower density (22.52 g cm-3) as compared to iridium
(22.61 g cm-3). Thus, iridium has the highest density among transition metals.
(vii) Reactivity d-block elements are less reactive due to high ionisation energies.
(viii) Complex formation: They are well known to form a large number of complex compounds
mainly due to (a) small atomic size and high nuclear charge (b) presence of partly filled or
vacant d-orbitals, e.g., K4[Fe (CN)6]
(ix) Coloured ions Colour exhibited by transition metal ions is due to the presence of unpaired
electrons in d-orbitals and is due to the d-d transitions of electrons, when invisible light is
incident on the ion. Colour of a complex depends on the metal, its oxidation state and its
ligands, e.g., [Cu(H2O)4]2+ is pale blue while [Cu(NH3)4]2+ is dark blue.
(x) Magnetic properties Paramagnetic nature is due to the presence of unpaired electrons in
d-orbitals. Magnetic moment is given by μ = √n (n + 2) BM, Where, n = number of unpaired
electrons and BM = Bohr magneton (unit of magnetic moment).
(xi) Catalytic properties the transition metals and their compounds behave like catalyst due
to
➢ the presence of partly filled d-orbitals resulting in variable oxidation states.
➢ formation of intermediate complex with reactants by lowering the energy of
activation.
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➢ their rough surface area which provides active sites for adsorption of reactant
molecules.
Iron in the preparation of NH3 (Haber‘s process).
(xii) Formation of alloys d-block elements have a strong tendency to form alloys.
(xiii) Interstitial compounds: The vacant space present in a crystal lattice is known as
interstitial site or void. The non-metal atoms (e.g., H, N, C, etc.) due to their small size when
occupy such place, the resulting compound is known as interstitial compound.
(xiv) Non-stoichiometric compounds can be formed due to the variability of Oxidation state
in the transition metal. These elements form such compound by trapping H, B, C and N etc.
(xv) Oxides and Oxoanions of Metals: The transition metals react with a number of non-
metals like oxygen, nitrogen, sulphur and halogens to form binary compounds. The first series
transition metal oxides are generally formed from the reaction of metals with oxygen at high
temperatures. These oxides dissolve in acids and bases to form oxometallic salts. Potassium
dichromate and potassium permanganate are common examples. Potassium dichromate is
prepared from the chromite ore by fusion with alkali in presence of air and acidifying the
extract. Pyrolusite ore(MnO2) is used for the preparation of potassium permanganate. Both
the dichromate and the permanganate ions are strong oxidising agents.
Preparation of potassium dichromate:
Structure of Chromate and Dichromate ion:
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Chromates and dichromates are interconvertible depending upon the pH of the solution:
Potassium dichromate is used as a primary standard in volumetric analysis. In acidic solution,
its oxidising action can be represented as follows:
Preparation of potassium dichromate:
A few important oxidising reactions of KMnO4 are given below:
1. In acid solutions:
Fe2+ ion (green) is converted to Fe3+ (yellow):
2. In neutral or faintly alkaline solutions: A notable reaction is the oxidation of iodide to
iodate:
Inner-Transition Elements: The elements in which the filling of atomic orbitals by electrons
take place in antepenultimate shell, two levels inside the outer subshell, are known as inner-
transition elements. They are also known as f-block elements.
They have been classified into two series.
(a) 4f-series (first inner-transition series) The last electron enters in 4f-orbital. The elements
belonging to this series are also known as lanthanoids.
(b) 5f-series (second inner-transition series) The last electron enters in 5f-orbital. The
elements belonging to this series are also known as actinoids.
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Lanthanides The fifteen elements from lanthanum (at. no. 57) to lutetium (at. no. 71) are
known as lanthanides or rare earths. Their properties are as follows:
1. Electronic configuration: The general electronic configuration of these elements is
[Xe]4f0–14 5d0-1 6s2.
2. Oxidation state: The most common and most stable oxidation state of lanthanides is +3
but some elements also exhibit +2 and +4 oxidation states.
3. Chemical reactions of the lanthanoids
Lanthanoid contraction
Steady decrease in the atomic and ionic (Ln3+) radii as the atomic number of the lanthanide
elements increases is called lanthanide contraction. This is because the additional electron
goes to 4f-subshell and 4f-orbitals being large and diffuse, have poor shielding effect. The
effective nuclear charge increases whichcauses the contraction in the size of electron charge
cloud. This contraction in size is quite regular and is known as lanthanoid contraction.
Consequences of lanthanoid contraction
(i) Covalent character of cations increases.
(ii) The electronegativity of trivalent ions increases slightly.
(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.
(iv) There is small increase in standard electrode potential values.
(v) Sizes of Zr and Hf; Nb and Ta are similar, so they are called chemical twins.
Actinoids: The actinoids include the fourteen elements from Th to Lr. The chemistry of the
actinoids is more complex in view of their ability to exist in different oxidation states.
Furthermore, many of the actinoid elements are radioactive which make the study of these
elements rather difficult.
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Their properties are as follows:
1. Electronic configuration: The general electronic configuration of these elements is
[Rn]865f1-146d0-17s2.
2. Oxidation state: Actinoids exhibit a greater range of oxidation states. This is because the
5f, 6d, and 7s levels are of comparable energies. Again, (+3) is the principal oxidation state for
actinoids.
3. Atomic and ionic sizes: Both lanthanoids and actinoids show decrease in size of their atoms
or ions in +3 oxidation state. In lanthanoids, the decrease is called lanthanoid contraction
whereas in actinoids, it is called actinoid contraction.
4. Chemical reactivity: Actinoids are highly reactive metals, especially when they are finely
divided. When they are added to boiling water, they give a mixture of oxide and hydride.
Actinoids combine with most of the non-metals at moderate temperatures. Alkalies have no
action on these actinoids. In case of acids, they are slightly affected by nitric acid (because of
the formation of a protective oxide layer).
There are many useful applications of the d- and f-block elements and their compounds,
notable among them being in varieties of steels, catalysts, complexes, organic syntheses, etc.
highly useful compounds in industry.
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